Complexed metals bonded to inorganic oxides

ABSTRACT

Complexed metals bonded to inorganic oxides are a new class of heterogeneous catalysts which display high upper reaction temperature limits, exceptional chemical and thermal stability and good catalytic activity for organic compound conversion. The catalyst of this invention comprises a substrate having a minimum surface area of about 10 m 2  /g and having pores with a minimum pore diameter of about 5 Angstrom Units, said substrate being modified by at least one amine functional member coordinated to a metal function, said amine functional member acting as a bridging member between said substrate and said metal function. 
     Also herein provided is a novel method of organic compound conversion which comprises contacting said organic compound with a catalytic amount of the above catalyst under organic compound conversion conditions.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a new class of heterogeneous catalyst havingexceptional chemical and thermal stability, high upper reactiontemperature limits and good catalytic activity for conversion of organiccompounds which comprises a substrate which is modified by at least oneamine functional member coordinated to a metal function, said aminefunctional member acting as a bridging member between said substrate andsaid metal function and organic compound conversion therewith.

2. Description of Prior Art

There has long been a need for effective, commercially practicabletransition metal catalysts for such reactions as hydrogenation,hydroformylation, carbonylation, dimerization and others. Earlycatalysts developed for such purposes were homogeneous catalysts whichsuffered from, among other things, the expense of recovering,repurifying and recycling said catalysts. Changes in selectivity andreactivity were often brought about by varying ligands and by changes inoperating conditions, such as, for example, temperature, pressure,reactant ratios, reaction rates and others. Catalyst losses were oftenso high that relatively inexpensive metals such as cobalt were used,even though such catalysts required severe operating conditions.Catalysts which were effective under somewhat milder conditions, such asrhodium complexes, were much more expensive (of the order of 10³ timesas expensive), and, therefore, to insure low catalyst loss, created therequirement of costly recovery systems.

More recently, a number of heterogeneous catalysts have been developed(Belgium Pat. No. 721,686) which demonstrate activities andselectivities for certain reactions, such as, for example,hydroformylation. Those heterogeneous catalysts are comprised oftransition metal complexes on ligands bonded to macroporous resins andshow superior catalytic results in certain reactions, such ashydroformylation, when compared to their homogeneous anologues. However,the utility of said heterogeneous catalysts is limited by the relativelylow chemical and thermal stability of the resin supports therein.

Another class of heterogeneous catalyst has been developed comprisingcomplexed transition metals on phosphine ligands bonded to inorganicoxide surfaces (Dutch Pat. No. 7,018,453 and British Pat. No.1,275,733). This class of catalysts has been shown to be useful in thehydroformylation reaction (Dutch Pat. No. 7,018,322).

The instant invention of a new class of heterogeneous catalysts, whichcatalysts comprise a substrate having a minimum surface area of about 10m² /g and having pores with a minimum pore diameter of about 5 AngstromUnits, said substrate being modified by at least one amine functionalmember coordinated to a metal function, said amine functional memberacting as a bridging member between said substrate and said metalfunction, are demonstrated to have chemical and thermal stabilityunmatched by prior resin-bound heterogeneous catalysts or oxide-boundphosphine functionalized heterogeneous catalysts. Further, the catalystof this invention has enhanced organic compound conversion activity,e.g. olefin isomerization activity, relative to other oxide-bound orresin-bound complexes. Still further, and with respect to catalyticactivity, the present catalyst shows dual-functional catalytic activity,e.g. in which an olefin is hydroformylated to an aldehyde which is thenconverted by an acid functionality of the catalyst to an acetal in thepresence of an alcohol.

SUMMARY OF THE INVENTION

In accordance with the present invention there is provided a newcomposition of matter comprising a substrate consisting of a poroussolid refractory inorganic oxide or zeolite having a minimum surfacearea of about 10 m² /g, preferably a minimum of about 200 m² /g, andhaving pores with a minimum pore diameter of about 5 Angstrom Units,preferably a minimum of about 100 Angstrom Units, said substrate beingmodified by at least one amine functional member coordinated to a metalfunction, said amine functional member acting as a bridging memberbetween said substrate and said metal function.

A further embodiment of the present invention consists of a novel methodor organic compound conversion which comprises contacting said organiccompound with a catalytically effective amount of the catalyst of thisinvention under organic compound conversion conditions.

DESCRIPTION OF PREFERRED EMBODIMENTS

The catalyst of the instant invention is a new class of heterogeneouscatalysts displaying exceptionally valuable properties in organiccompound conversion processes. The catalyst hereby provided comprises asubstrate having certain specific and essential modifications. Thesubstrate may be one of a number of solid porous inoganic oxides orzeolites having surface hydroxyl groups, provided that said inorganicoxides has a minimum surface area of about 10 m² /g and pores with aminimum pore diameter of about 5 Angstrom Units. Non-limiting examplesof said substrate include those having a major component of silica oralumina or both, such as, for example, alumina, siliceous materials,open lattice clays and crystalline aluminosilicates.

Non-limiting examples of siliceous materials useful as said substrateinclude silica and combinations thereof with oxides of metals of GroupsII-A, III-A, IIIB, IVA, IV-B and V-B of the Periodic Table of Elements,such as, for examle, silica-alumina, silica-magnesia, silica-zirconia,silica-thoria, silica-berylia, silica-titania, as well as ternarycompositions of silica, such as, for example, silica-alumina-thoria andsilica-alumina-zirconia.

Non-limiting examples of crystalline aluminosilicate materials useful asthe substrate of the present catalyst include the synthetic zeolites X,Y, ZSM-4, ZSM-5, ZSM-11, ZSM-21 and others, and naturally occurringzeolites, such as erionite, faujasite, mordenite and others.

Non-limiting examples of open lattice clays useful as the substrate ofthe present catalyst include bentonite and montmorillonite and others.

The solid porous refractory oxide for use herein as said substrate mayhave deposited or exchanged thereon one or more of various metalcomponents in keeping with the spirit and scope of the invention. Forexample, alumina and a siliceous material as above defined may havedeposited thereon a metal of Groups VIB or VIII of the Periodic Table ofthe Elements, e.g. Co and Mo, or an oxide of such a metal, e.g. MoO₃ andCrO₃. Also, for example, a crystalline aluminosilicate for use hereinmay have exchanged thereon hydrogen or metal cations of Group IA-VIII ofthe Periodic Table, especially metals of Groups II and III, includingthe rare earth metals, tin, lead, metals of the actinide series,antimony, bismuth and chromium or combinations thereof. Further, acrystalline aluminosilicate for use herein may be incorporated into anaturally-occurring inorganic material, such as, for example clay andmetal oxides.

Specific modifications to the substrate chosen for the present catalystinclude at least one amine functional member coordinated to a metalfunction, said amine functional member acting as a bridging memberbetween said substrate and said metal function. Said amine functionexists, when in a bridging position between said substrate and saidmetal function, as a ligand covalently bonded to said substrate. Thefunctionalization, i.e., covalently bonding said amine ligand to saidsubstrate, of said substrate can be either exterior or interior of saidsubstrate.

The metal function complexed to said amine ligand bridging member may beany one or more of a series of metals recognized in the art astransition metals. Non-limiting examples of such metals include themetals of Groups VIII and IB of the Periodic Table of Elements, such as,for example, iron, cobalt, nickel, ruthenium, rhodium, palladium,iridum, platinum, silver, gold, copper and osmium; rare earth metals;scandium; titanium; vanadium; chromium; and manganese.

Said metal functions for complexing to said amine ligand functions maybe in the form of, by way of non-limiting example, halides, e.g.fluorides, chlorides and iodides, oxides, sulfides, sulfates,carbonates, carboxylates and nitrates.

Non-limiting examples of said catalyst, therefore, include thefollowing, wherein X is said complexed metal function: ##EQU1## ##SPC1##

In synthesis of the catalyst of the present invention the general methodmay be employed in which a suitable substrate, i.e. a porous solidinorganic refractory oxide, having surface hydroxyl groups, e.g.,silica, silica-alumina, alumina, a natural zeolite such as, for example,erionite, and a synthetic zeolite such as, for example, ZSM-5, isallowed to react with a suitable alkyl substituted compound of group IVAof the Periodic Table, in acid or base catalysis, if desired. The abovealkyl compounds must contain a functional group on the central group IVAatom, preferably silicon, as for example, hydro, amino, amido, carboxy,alkoxy or halogen which will condense with hydroxyl groups to give acovalent bond. Said alkyl compound must also have on the alkyl moietyone or more ligands (or groups which may be converted to ligands viaconventional organic chemistry) suitable for bonding transition metalcomplexes which have desirable catalytic properties, such as, forexample, rare earth metals, Fe, Co, Ni and the platinum group metals.

More specifically, the method of preparing a catalyst of the presentinvention may include suspending said porous solid inorganic oxidesubstrate in a solution of an appropriate amino alkyl substitutedcompound of Group IVA, for example, a silane, in xylene or anothersuitable solvent, refluxing the resulting mixture for a suitable time,such as, for example, 2-6 hours, cooling the mixture and washing it witha suitable solvent, such as, for example, hexane, in which said silaneis soluble, and then drying the resultant product in a vacuum, such as,for example, in a vacuum oven, at an elevated temperature of, forexample, 100°C. to about 150°C. The individual steps of this method maybe separated by long periods of time without detrimental results.

For preparation of the insoluble oxide-bound metal compound complex, asolution of soluble coordination compound having at least two ligandsconnected to at least one central metal atom is mixed with the insolublefunctionalized oxide. Upon mixing of the coordination compound with thefunctionalized oxide, the two react with the functional group of theoxide replacing one or more of the ligands of the coordination compound,thereby chemically bonding the coordination compound to the oxidethrough at least one bond which joins the central metal atom to afunctional group.

The ligands of the soluble coordination compound may be ionic, neutralor mixed ligands. Anionic ligands include chloride, bromide, iodide,cyanide, nitrate, sulfate, acetate, sulfide, and trichlorostanniteligands. Neutral ligands include water, ammonia, phosphine, carbonmonoxide, olefin, and diolefin ligands.

The central metal atom of the soluble coordination compound may beplatinum, palladium, rhodium, ruthenium, osmium, iridium, gold, cadmium,titanium, zirconium, hafnium, vanadium, chromium, molybdenum, tungsten,manganese, rhenium, iron cobalt, nickel, copper, zinc, silver, andmercury. Preferably, the central metal atom is a metal of the platinumseries, namely, platinum, palladium, rhodium, ruthenium, osmium, andiridium. Usually, the soluble coordination compound will have onecentral metal atom. However, it may have two central metal atoms, eitherthe same or different.

Examples of suitable coordination compounds are potassiumtetrachloropalladite, chloroplatinic acid, rhodium trichloridetrihydrate, dichlorobis (triphenylphosphine) palladium (II),dichlorotetrakis-(triphenylphosphine) ruthenium (II),chlorobis(triphenylphosphine) rhodium (I), tricarbonylbis(triphenylphosphine) ruthenium (O), iodocarbonylbis (triphenylphosphine)iridium (I), potassium tetranitroplatinate (II), potassiumtetrahydroxoaurate (III), sodium oxotetrafluorochromate, tetra(pyridine) platinum (II) tetrabromoplatinate, tetraaminepalladium (II)chloride, di-mu-chlorodichlorobis (triethylarsine) diplatinum (II),di-mu-thiocyanatodithiocyanatobis(tripropylphosphine) diplatinum (II)and potassium trichloro (trichlorostannato) platinite (II).

Solvents for the soluble coordination compounds include water, methanol,ethanol, butanol, acetic acid, chlorinated hydrocarbons such aschloroform, various ethers such as diethyl ether, acetone, and dimethylsulfoxide.

The solution of the soluble coordination compound and the functionalizedoxide, upon mixing, is subjected to agitation at a temperature and for atime to effect bonding of a desired amount of the coordination compoundto the functionalized oxide. Agitation may be effected simply bystirring. However, other conventional means of agitation may beemployed. The temperature may range from between room temperature tojust below the decomposition temperature of either the coordinationcompound or the amine functional bridging member. Preferably,temperatures between room temperature and the boiling point of thesolvent for the coordination compound are employed. The rate at whichthe coordination compound reacts with the functionalized oxide depends,of course, on the temperature, the rate increasing with temperature. Thetime of agitation may range from a fraction of an hour, say one-quarterof an hour, to several hours, say 12 hours, or even one or more days,say three days.

Following reaction of the coordination compound and the functionalizedoxide, the resulting insoluble oxide-bound metal compound complex isseparated from the product mixture. Separation may be by anyconventional means. Thus separation may be by settling of the complexand decantation of the liquid portion of the product mixture. Separationmay also be made by filtration or centrifugation. The complex then maybe washed to removed adhering and absorbed solvent and any unreacteddissolved coordination compound. Washing, for example, may be withwater, followed by ethanol, and then with ether. Thereafter, the complexmay be dried.

The insoluble oxide-bound metal compound complex will be insoluble inthe materials, heretofore mentioned, in which the original oxide portionof the complex is insoluble. Thus, the complex will be insoluble inwater, hydrocarbons such as benzene, alcohols, aldehydes, ethers,ketones, organic acids, carbon disulfide, thiols, amines, and others.Further, the metal of the coordination compound being bonded chemicallyto the functionalized oxide will also be insoluble in these samematerials.

The final catalyst may comprise 0.01 to 30 percent, preferably 0.1 to 10percent, by weight of metal; 0.1 to 25 percent, and preferably 2 to 10percent, by weight of amine-functional ligand; and about 60 to 99.9percent by weight of oxide. The sum of the amount of the ligand andmetal preferably should not exceed 25 percent.

The production of an insoluble oxide bound metal compound complex may beillustrated employing, as a soluble coordination compound having anionicligands, potassium tetrachloropalladite, K₂ PdCl₄, and, an insolublefunctionalized silica. The coordination compound is dissolved in waterand then mixed with the functionalized oxide. The coordination compoundreacts with the functionalized oxide according to the followingequation: ##EQU2## The K⁺ is not chemically bonded to the Pd. Thecomplex of equation (1) may then react as follows:

The insoluble oxide-bound metal compound complexes may be seen tocomprise an insoluble functionalized oxide containing basic functionalgroups and chemically bonded to some of the functional groups are metalatoms, the metals having been set forth hereinabove. The bonding occursas a result of coordination of the functional group of the oxide to themetal. The metal atoms preferably have chemically bonded thereto atleast one ligand, the ligands also having been set forth hereinabove.For example, the insoluble metal compound complex set forth in equation(2) has two Cl ligands connected to the Pd atom and also two functionalgroups. Further, it could have one Cl ligand and three functionalgroups, or, as in the complex of equation (1), three Cl ligands and onefunctional group. On the other hand, the insoluble metal compoundcomplexes may have a total of three, five, six, seven, or eight ligandsand functional groups. At least one functional group must be present.

The insoluble oxide-bound metal compound complex is furthercharacterized by its quantitive composition as set forth above.

The insoluble oxide-bound metal compound complexes are suitable for useas catalysts in carrying out catalyzed reactions. Said reactions arethose which are catalyzed by soluble compounds of the metals set forthhereinbefore in homogeneous catalysis. Preferably, the insolubleoxide-bound metal compound complexes are employed as catalysts. Forexample, they are useful in hydrogenation reactions involving compoundshaving carbon-to-carbon unsaturation, as in the conversion ofacetylenes, olefins, and diolefins, using complexes containing compoundsof platinum, palladium, ruthenium, rhodium, and other metals. Forcarrying out catalytic reactions generally, complexes containing as thecentral metal atom any of the metals described in the precedingparagraphs are of use.

Other catalytic reactions in which the oxide-bound metal compoundcomplexes are of value include carbon monoxide-insertion reactions,double bond isomerizations, vinyl ester interchange reactions, andolefin (e.g. ethylene) oxidation reaction. Other reactions includeolefin hydroformylation, comprising the reaction of an olefin withcarbon monoxide and hydrogen in the presence of complexes containingnickel, cobalt, or rhodium carbonyl moieties; olefin dimerization andpolymerization in the presence of nickel or rhodium chloride-containingcomplexes; olefin hydrocarboxylation, hydroesterification, andhydrocyanation in the presence of complexes containing a metal carbonylmoiety, or metal hydrocarbonyl moiety, or metal phosphine-substitutedcarbonyl moiety; conversion of CO and H₂, or alcohol and CO and H₂, tomixtures of hydrocarbons and/or alcohols; hydroquinone synthesis fromacetylenes, carbon monoxide, and water; or the cyclooligomerization ofacetylene to benzene and the like; the cyclooligomerization of butadieneto cyclooctadiene; or the carbonylation of acetylenes and olefins toacids. Also, acetylenes may be hydrated over rutheniumchloride-containing complexes. It will be apparent that many of thesereactions involve the conversion of unsaturated compounds, particularlyof unsaturated hydrocarbons like olefins and acetylenes. Referring againto ethylene oxidation, this reaction may be run in several ways; thus,ethylene may be oxidized in aqueous solution to produce acetaldehyde, orit may be oxidized in methanol solution to give vinyl methyl ether, orin acetic acid solution to produce vinyl acetate.

In view of the fact that the complex may contain some functional groups,i.e., basic groups, as well as metal compound groups, it follows thatthe complex may be a dual functional catalyst containing two types ofsites, basic sites and metal compound sites. Functionalized zeolites cancontain acidic sites in addition to the metal compound sites. It is thususeful to catalyze polystep catalytic organic reactions at lowtemperature and in the liquid phase. In such a reaction, one type ofcatalytic site catalyzes a reaction step different from that catalyzedby another type of site. The different types of sites are separated bydistances of the order of molecular dimensions.

In some reactions, both liquid and gaseous reactants take part and aresuitably catalyzed by the complexes. In all reactions, ease of catalystseparation by conventional operations of filtration, decantation, orcentrifugation is a characteristic, whether the products and/orreactants are liquid or gaseous. The reactions may be carried out inconventional fixed bed flow reactors, or in continuously stirred flowreactors, or in batch reactors. Pressure may range to 300 atmospheres ormore, and reaction times from less than one minute to several hours.

It is noted that a particular advantage of oxide-bound metal complexesis their high thermal stability which allows their use in reactions attemperature in which liquid phase is not easily obtained or attemperatures which would be high enough to degrade or collapse the porestructure of polymer-bound metal complexes. Also, an advantage of theamine functional groups, in comparison with phosphine functional groups,is the high oxidative stability of the former.

In order to more fully illustrate the present invention, the followingspecific examples are presented. Said examples, it will be appreciated,are not meant to be, and should not be taken as, unduly limiting in anyway.

EXAMPLE 1

A 50 gram portion of small-pore silica was suspended in 250 ml. ofxylene containing 10 ml. of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane. It was then heated to reflux (approx.69°C) for four hours and cooled to room temperature. The solvent wasdecanted and the product was washed three times with 250 ml. portions ofn-hexane. The product was then suspended in 125 ml. of 88% formic acidand 100 ml. of 37% formaldehyde. The resulting suspension was refluxedfor 6 hours and cooled. The solvent was decanted and the product washedwith water until neutral and then boiled in 300 ml. of water for onehour. The water was then decanted and the product washed two times with300 ml. portions of acetone and dried in a vacuum oven at 125°C for twohours. Yield was 53.8 grams of substance having the structural formula:##EQU3##

Analysis of the above product showed 0.3% N.

Five grams of the above functionalized oxide product was suspended in150 ml. benzene through which CO had been bubbled for 15 minutes. A 0.15gram portion of [Rh(CO)₂ Cl]₂ was completely dissolved therein and themixture was warmed to 50°-55°C for 16 hours and then cooled. The brownproduct was filtered out, washed and dried. Analysis of this productshowed 1.86%C, 1.63%H and 0.26%Rh.

EXAMPLE 2

A 15.0 gram portion of the functionalized oxide of Example 1 wassuspended in 200 ml. benzene through which CO had been bubbled for 15minutes. A 0.83 gram portion of [Rh(CO)₂ Cl]₂ was completely dissolvedin this system. The resulting mixture was then heated to 50°-55°C for 16hours and cooled. The brown product was discernable from the clear,colorless supernatant solution and was filtered out, washed withbenzene, methanol and petroleum ether, and dried under vacuum at 120°Cfor 1/2 hour. Analysis of this product showed 1.86%C, 1.63%H and0.81%Rh.

EXAMPLE 3

A 50 gram portion of a commercial large-pore silica was suspended in 300ml. concentrated HCl; the mixture was heated to reflux (107°C) for 4hours and then cooled. The silica was filtered out, washed withdistilled water until the wash water was neutral, washed with acetone,and dried in a vacuum oven at 125°C for 16 hours. Yield was 47.75 grams(loss was probably mechanical). This material was then suspended in 300ml. toluene; 27.5 grams dichlorodimethylsilane was dissolved in 100 ml.toluene and added. The mixture was then heated to reflux (104°C) for 4hours and cooled. The mixture was reduced to a volume of 100 ml. on arotary evaporator at about 90°C and about 20 mm. Hg pressure. A 10 gramportion of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane was dissolvedin 100 ml. toluene and added to the above mixture. All volatile liquidswere then removed by distillation in a rotary evaporator. Yield was 56.4grams. An 18.3 gram portion of this material was placed in a glass tubeand heated to 150°C for 2 hours while air was drawn through the tube atabout 1 liter/minute. Yield was 17.7 grams. This product was thensuspended in 45 ml. of 91% formic acid and 36 ml. of 37% formaldehydesolution. The mixture was stirred and heated to reflux (89°C) for 6hours and then cooled. The product was filtered out and washed withdistilled water until the wash was neutral. It was then stirred in waterat 90°C for 1 hour, filtered, washed with acetone and dried in a vacuumoven for 3 hours. Yield was 15.1 grams (most loss was probablymechanical). Analysis of this product showed 3.54%C, 1.05%H, and 0.5%N.

The initial step of refluxing in HCl was to convert some surfacehydroxyl groups to surface chloride groups and thus activate the surfacefor condensation reactions. The condensation with dimethyldichlorosilanecreates a surface on which some pairs of surface hydroxyls or chloridesare converted to surface methyls as follows: ##EQU4## This made thesurface less acidic and partially changed it from hydrophilic tohydrophobic. In addition, the following modifications resulted: ##EQU5##This produced a site good for further condensation since it is flexibleand reduces steric requirements in the next step and also causes thefinal ligands to be farther away from the surface.

The procedure for putting on the amine ligand gave a product in which(1) the aminosilane was partially polymerized (at the silane end) as itwas deposited, and (2) this polymer was connected to the surface throughmore than one of the above flexible sites (and possibly to originalsurface sites as well). The result was a more firmly bonded ligandbecause a number of siloxane bonds would have to be broken for an aminefunction to be removed.

For the preparation of a catalyst, 5.0 grams of the above product wassuspended in 150 ml. benzene through which CO had been bubbled for 15minutes. A 0.16 gram portion of [Rh(CO)₂ Cl]₂ was completely dissolvedin this system; the mixture was warmed to 50°-55°C for 6 hours andcooled. The product was brown and the supernatant solution clear andcolorless. The product was filtered out, washed with benzene, methanoland petroleum ether, and dried under vacuum at 120°C for 1/2 hour. Yieldwas 4.9 grams (most loss probably mechanical). Analysis of this productshowed 0.81% Rh.

EXAMPLE 4

To 50 grams of silica suspended in 250 ml. xylene was added 10.4 gramsN-(β-aminoethyl)-γ-aminopropyltrimethoxysilane and 0.1 gramp-toluenesulfonic acid. The mixture was stirred under reflux for 4hours, cooled, washed with n-hexane, and dried in a vacuum oven at 120°Cfor 16 hours. This material was then suspended in 100 ml. 88% formicacid and 75 ml. 37% formaldehyde and stirred under reflux for 16 hours.After cooling to room temperature, 100 ml. 0.1N HCl was added and themixture stirred for 10 minutes. The silica was filtered out, suspendedin water; 1N NaOH was added until the solution was neutral; and thesilica was then filtered out and washed with 1 liter of water. Thesilica was resuspended in 400 ml. water and the mixture was concentratedby evaporation at approximately 100°C to about half of the originalvolume. (This step is designed to remove any silane not covalentlybonded to the silica). The silica was then filtered out and dried in avacuum oven at 120°C overnight. The product contained 4.06% C and1.12%N.

Carbon monoxide was bubbled through 100 ml. benzene for 15 minutes, 1.29gram Rh₂ (CO)₄ Cl₂ was dissolved in the benzene by warming, and 9.0grams of the above functionalized silica was added. The mixture wasstirred at 60°C for 16 hours, and the silica was filtered out, washedwith benzene and dried in a vacuum oven at 130°C for 2 hours. Theproduct contained 6.84% rhodium.

EXAMPLE 5

This catalyst was prepared as in Example 4 through the step prior torhodium incorporation. It was further treated as described below toconvert any free surface silanol groups to trimethylsilyl groups beforethe rhodium was incorporated. Twenty-five grams of catalyst wassuspended in 250 ml. dried xylene and 10 ml. N,O-bis(trimethylsilyl)-acetamide was added with stirring. The mixture wasmaintained at 100°C for 4.5 hours and then at 50-55%C for 16 hours. Thesilica was filtered out, washed with boiling water to remove acetamide,rinsed with acetone and dried in a vacuum oven. Rhodium was then addedin the same way as in Example 3. The final product contained 4.55% C,0.87% N, and 1.96% Rh.

EXAMPLE 6

Thirty grams silica, 6.25 grams N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and 120 ml. benzene were charged to a 300ml. autoclave and heated to 300°C (approx. 900 psi) with stirring for 3hours. After cooling, the product was washed as after the condensationstep in Example 4, and the synthesis was continued as in Example 4,except that a lower loading of rhodium was added. The final productcontained 4.00% C, 0.55% N, and 1.26% Rh.

EXAMPLE 7

This catalyst was prepared from a portion of an intermediate materialmade in the preparation of the catalyst of Example 6, so the preparationwas the same up to the incorporation of the metal salt. An 8.0 gramportion of the silica that had been treated with N-(β-aminoethyl)-γ-aminopropyltriethoxysilane and then with a formic acid/ formaldehydesolution followed by the usual work-up was then suspended in 100 ml. ofa 1/1 (vol./vol.) mixture of methanol/acetone through which carbonmonoxide had been bubbled for 0.25 hour. Then 0.2 gram Ru (CO)₂ Cl₂ wasadded and the mixture was warmed with stirring to reflux temperature(58°C.). Bubbling of CO through the system was continued, an additional100 ml solvent was added, and reflux was continued for 16 hours. Thesilica was filtered out, washed thoroughly with methanol, and dried invacuo at 125°C for 0.5 hour. The catalyst contained 4.5% carbon, 0.94%hydrogen and 0.6% nitrogen.

EXAMPLE 8

This catalyst was prepared from a portion of an intermediate materialmade in the synthesis of the catalyst of Example 5. A 12.0 gram portionof material was removed from the preparation of the catalyst of Example5 just prior to the treatment with N,O-bis (trimethylsilyl)-acetamide.Instead, it was suspended in 300 ml. benzene through which carbonmonoxide had been bubbling for 0.25 hour and 0.15 gramdicobaltooctacarbonyl was added. Bubbling of CO was continued and themixture was heated to 62°C for 0.5 hour, cooled, washed thoroughly withhexane and petroleum ether and dried. The product contained 4.50%carbon, 1.23% hydrogen, 1.1% nitrogen, and 0.42% cobalt.

EXAMPLE 9

Gamma-Alumina was made by heating α -alumina for 3 hours at 900°F inair. This material was treated with N-(β-aminoethyl)-γ-aminopropyl-trimethoxysilane by the procedure of Example4 and then treated with formic acid/formaldehyde and worked up, also bythe procedures of Example 4. It was then treated withN,O-bis(trimethylsilyl)-acetamide by the procedure of Example 5 and thenwith Rh₂ (CO)₄ Cl₂ by the procedure of Example 4. The final productcontained 15.0% carbon, 2.2% hydrogen, 0.32% nitrogen and 0.33% rhodium.

EXAMPLE 10

A 10 gram sample of synthetic zeolite Y is suspended in water for 4hours and removed by filtration but allowed to stay wet and thensuspended in 4 ml N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, 0.03grams p-toluenesulfonic acid, and 60 ml xylene. The mixture is stirredunder reflux for 16 hours. The sample is filtered out, washed withn-hexane, and dried in a vacuum oven. It is then suspended in 200 ml.benzene through which CO has been bubbled for 15 minutes. A 0.8 gramportion of [Rh(CO)₂ Cl]₂ is added to the suspension. The resultingsystem is heated to 50°-55°C for 16 hours with continuing CO flow. Theproduct is filtered out, washed with benzene, methanol, and petroleumether and dried under vacuum at 120°C for 4 hours.

EXAMPLE 11

A substituted aminosilane functionalized silica was prepared as follows:

Three hundred grams of silica gel was suspended in xylene and heated tothe reflux temperature. To this was added 45 grams of chloromethylmethyl silane and the mixture was stirred and heated at refluxovernight. The mixture was cooled to about 50°C; 10.0 ml oftrimethylchlorosilane was added and the mixture was allowed to cool andstand overnight. The product was isolated by filtration and washed withxylene, hexane, and petroleum ether and was found by analysis to contain2.73% Cl, 2.07% C, and 0.71% H on a weight basis.

Sixty ml. (24.7 grams) of the above product was further modified bysuspending it in 60 ml. of dimethylformamide and 22.5 grams ofethylamine and heating to 150°C for 10 hours. The reaction mixture wascooled and the product isolated by filtration. It was then washedsequentially with hexane, water, dilute NH₄ OH, water, 1% HCl, water,dilute NH₄ OH, 2% NaOH, water (until neutral), methanol, and petroleumether. Analysis of the final product showed it to contain on a weightbasis 0.18% N, 1.0% C, and 0.61% H.

Ten grams of the above amine functionalized silica was further modifiedby suspending it in 50 ml. of chloroform containing 10 ml. ofethylamine. To this stirred mixture was slowly added 5.0 ml. ofbis-isopropylchlorophosphine. The reaction mixture was allowed to standovernight, the product was isolated by filtration, and washedsequentially with chloroform and petroleum ether, and dried under N₂.The final product was analyzed and found to contain on a weight basis5.1% C, 1.5% H, 0.6% Cl, 0.13% N, and 1.1% P.

EXAMPLE 12

The functionalized silica of Example 11 was used to make a catalyst forthe dimerization of propylene. Fourteen ml. (5.4 grams) of thefunctionalized silica was suspended in 100 ml. of chlorobenzene and 100ml. of a 0.0026 M solution of Ni(acac)₂ in chlorobenzene was added. Thesolution was refluxed with gentle stirring for two hours and cooled. Thesupernatent liquid was decanted in a drybox and the solid, after washingwith 100 ml. chlorobenzene, was vacuum dried. Analysis on a weight basiswas 0.84% P, and 0.24% Ni.

The catalysts of the present invention are useful in organic compoundconversion, such as, for example, hydroformylation, oxidation,oligomerization, dimerization, hydrogenation, Fischer-Tropschhydrocarbon synthesis and others. They exhibit excellent thermalstability up to a termperature of about 400°C, while the heterogeneousresin catalysts are stable only up to about 200°C.

For the purpose of illustrating organic compound conversion utilizingthe present catalyst, the following test procedure was adapted:

Each test was conducted in a stirred 300 ml. autoclave whereby liquidsand gases could be added and removed while the autoclave reaction systemwas under pressure. In each test, 1 to 2 grams of catalyst and 90 ml.solvent, e.g., benzene or 1:8 (volume/volume) methanol:benzene, werecharged to the reactor, which was then pressure-tested with CO andvented. The system was heated to reaction temperature and thenpressurized with 1:1 hydrogen:carbon monoxide. Then 20 ml. 1:11-hexane:n-octanal was added and the reaction started. Pressure wascontrolled at 1000 psi, or gas was added periodically so that thepressure fluctuated between about 900 and 1000 psi. Samples werewithdrawn and the total product analyzed by gas chromatography on aCarbowax 1000 column, and C₆ hydrocarbons on a TCP column. Liquidsamples were analyzed for Rh and N. Used catalysts were analyzed for Rh,C and N.

Since the formation of aldehydes and alcohols from olefins can be shownto conform to the following scheme, the absolute values of all the rateconstants of the reactions were determined. ##EQU6## The n-octanal wasincluded in the reaction mixtures for ease of kinetic evaluation of thecatalysts.

Assuming that aldehyde diacetals were in rapid equilibrium with thecorresponding aldehydes, the hydrogenation rate was measured by thedisappearance of the total thereof. ##EQU7## was a measure of thelinearity of the hydroformylation products from 1-olefin. ##EQU8## was acomparison of the rates of isomerization and hydroformylation of1-olefins. These two functions are important because in mostapplications normal aldehydes are preferred. S_(AC) was defined as thepercent diacetal in the linear product at the specified time. S_(AL) wasdefined as the ratio of the rate of "steady-state" alcohol formation tothe rate of steady-state total olefin conversion. The specific rateconstants k₁ and k₂, corrected for Rh loading, reaction volume, etc.,gave a measure of the relative activities of the catalysts tested.

Results of the organic compound conversion test hereinabove defined onthe catalyst samples prepared by examples herein are tabulated in TableI. For comparison, an amine functionalized polymer ##EQU9## was used asa catalyst as well. The table clearly shows somewhat lower activity forthe polymer catalyst and its lack of activity for the formation ofacetate.

                                      TABLE I                                     __________________________________________________________________________    Organic Compound Conversion Test.sup.(1) of Catalyst Species                  Catalyst of                                                                   Example                                                                              S.sub.L                                                                           S.sub.I                                                                           S.sub.AC.sup.(4)                                                                   S.sub.AL × 10.sup.3                                                            (k.sub.1 + k.sub.2) × 10.sup.3                                                   Time.sup.(5)                                                                       Conversion                           __________________________________________________________________________    3      75.6                                                                              55.8                                                                              1    0      357      2.5  99                                    3.sup.(2)                                                                           71.8                                                                              60.8                                                                              2.7  0      530      4.3  100                                  4      79.6                                                                              60.7                                                                              19   1.3    136      7.4  100                                   4.sup.(3)                                                                           71.5                                                                              82.8                                                                              --   2.8    52       21   98                                   5      71.2                                                                              63.5                                                                              31   approx. 1                                                                            910      2.5  99                                   6      74.8                                                                              46.8                                                                              0.2  9.4    396      2.0  99                                   9      73.1                                                                              56.3                                                                              0    --     1,237    2.0  99                                   (Polymer)                                                                            74  67  0    0      154      6.0  84                                   __________________________________________________________________________     .sup.(1) Hydroformylation of 1-hexene at 100°C, 1000 psi and with      methanol/benzene solvent.                                                     .sup.(2) Catalyst from above run re-used after cleaning by 1 hour reflux      in MeOH/benzene.                                                              .sup.(3) Hydroformylation of 1-hexene at 100°C, 1000 psi and with      benzene solvent.                                                              .sup.(4) At time indicated.                                                   .sup.(5) Time of run in hours.                                                .sup.(6) Total olefin conversion.                                        

EXAMPLE 13

Propylene was dimerized in a vertical downflow reactor over 2 cc of thecatalyst of Example 12 diluted with 2 cc of 50/80 mesh Vycor chips. Thecatalyst was first pretreated with a solution of 0.2 M (diethylamino)di-isopropyl phosphine at 0°C. A 58% propylene/42% propane mixture wasfed at a rate of 50 ml/minute over the catalyst together with a solutionof 0.052 M aluminum sesiquichloride in chlorobenzene at a rate of 7.3ml/hour. This corresponds to 3 WHSV based on total catalyst and 1250WHSV based on nickel. The conversion remained essentially constant atabout 50% for 6.5 hours and the selectivity of dimethyl butenes variedbetween 23 and 70%. Typical product compositions were 88% dimers, 8%trimers, and 4% higher oligomers.

To further illustrate an organic compound conversion process utilizingthe catalyst of the present invention, a Fischer-Tropsch reaction systemwas employed with catalysis therein by the catalyst hereof. Reactionconditions and results thereof are listed in Table II. Under thesetemperature conditions, a polymer bound metal complex would not beusuable because of the thermal instability of the polymer.

                                      TABLE II                                    __________________________________________________________________________    Catalyst of    Pressure,                                                                           psig.                                                                             Temperature,                                         Example                                                                              Reactants                                                                             H.sub.2                                                                             CO  °C                                                                            Time.sup.(1)                                                                       Yield.sup.(2)                            __________________________________________________________________________    7      1-butanol.sup.(3)                                                                     500   500 300    12.5 6.8                                      7      n-propanol                                                                            500   500 300    96   approx. 6                                7      1-hexene/                                                                             500   500 300    96   approx. 5.sup.(4)                               n-propanol                                                             8      1-octanol/                                                                            500   500 300    26   approx. 5.sup.(6)                               1-hexene.sup.(5)                                                       __________________________________________________________________________     .sup.(1) Reaction time in hours.                                              .sup.(2) Percent yield of products having a higher boiling point than the     reactants (not including hydroformylation products).                          .sup.(3) Benzene solvent.                                                     .sup.(4) Hydroformylation products also noted.                                .sup.(5) Methanol and 1,2,4-trimethylbenzene solvents.                        .sup.(6) Hydroformylation and olefin isomerization products also noted.  

What is claimed is:
 1. A catalytic material which comprises a substrateof a porous refractory oxide, said substrate having surface hydroxylgroups, a minimum surface area of about 10 m² /g and pores with aminimum pore diameter of about 5 Angstrom Units, said substrate beingmodified by at least one amine functional member, containing the elementsilicon, coordinated to a metal function of a transition metal selectedfrom the group consisting of Group VIII metals of the Periodic Table ofElements, said amine functional member acting as a bridging memberbetween said substrate and said metal function, as a ligand covalentlybonded to said substrate.
 2. The material of claim 1 wherein saidsubstrate has a minimum surface area of about 200 m₂ /g and has aminimum pore diameter of 100 Angstrom Units.
 3. The material of claim 1wherein said refractory oxide has a major component of silica oralumina.
 4. The material of claim 1 wherein said refractory oxide isselected from the group consisting of alumina, silica, silica combinedwith an oxide of a metal of Groups IIA, IIIA, IVA, IIIB, IVB or VB ofthe Periodic Table of Elements, open lattice clays and crystallinealuminosilicates.
 5. The material of claim 4 wherein said refractoryoxide is silica or silica combined with an oxide of a metal of GroupsIIA, IIIA, IVA, IIIB, IVB or VB of the Periodic Table of Elements. 6.The material of claim 4 wherein said refractory oxide is a crystallinealuminosilicate.
 7. The material of claim 6 wherein said crystallinealuminosilicate is a synthetic zeolite.
 8. The material of claim 6wherein said crystalline aluminosilicate is a natural zeolite.
 9. Thematerial of claim 5 wherein said refractory oxide is alumina.
 10. Thematerial of claim 1 wherein said substrate is silica and said metalfunction is rhodium or ruthenium.
 11. The material of claim 1 whereinsaid amine functional member is selected from the group consisting ofN-(β-aminoethyl)-γ-aminopropyltrimethoxsilane andN-(β-aminoethyl)-γ-aminopropyltriethoxysilane.